Germs resisting and self cleaning infiltration thin film and manufacturing method thereof

ABSTRACT

The invention provides a germs resisting and self-cleaning infiltration thin film and manufacturing method thereof. At first, a Polyethyleneimine (PEI) and a Polyvinyl Alcohol (PVA) are used to make a polymer thin film. Then, a germ resistant and an inorganic metal oxide are added into the polymer thin film to form the selective infiltration thin film capable of resisting germs and self-cleaning.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a thin film, and more particularly, to a selective infiltration thin film capable of resisting germs and self-cleaning and a manufacturing method thereof.

2. Description of the Prior Art

In recent years, with the highly development of the industry and commerce, although material enjoyments and life convenience are brought, there are also many new type of social problems such as environment pollution and occupational injury brought to human's life. Therefore, some procedures and equipments to solve or prevent these problems are generated consecutively.

With the progress of the times, common protective materials are also developed toward the multi-functional hybrid materials, the features of lightweight, flexible and durable, low cost, can be washed and can be re-used are emphasized, and the functions of breathable, blocking bacteria, viruses and poisons can be provided. However, at present, there are still considerable problems existed in the use of protective equipment and the following after treatment.

As to the protective clothing, reviewing the health care workers at various levels and military troops have taken part in the chemical help with the relief of the various major chemical hazard events during the past SARS period, it can be found that isolation protective clothing is indeed the necessary equipment for the first-line personnel. At present, most the common-used isolation protective clothing is made of nonwoven cloth to prevent that the health care workers are directly contaminated by liquid contaminants. However, since the isolation protective clothing of nonwoven cloth can not stop the penetration of the gas contaminants, and the viruses and poisons attached to the isolation protective clothing are not died or disappeared. Even the isolation protective clothing will be burned after being used to protect the Secondary pollution, however, there are still potential risks existed in the process of removing the isolation protective clothing after the use of a and cleaning staff, therefore, how to let the protective material have self-cleaning effect is a problem needed to be solved.

SUMMARY OF THE INVENTION

Therefore, a scope of the invention is to provide a selective infiltration thin film capable of resisting germs and self-cleaning and a manufacturing method thereof, so that the problems occurred in prior arts can be solved.

According to an embodiment of the invention, the selective infiltration thin film manufacturing method includes the following steps of: (a) using a Polyethyleneimine (PEI) and a Polyvinyl Alcohol (PVA) of appropriate ratio to make a polymer thin film; (b) adding a germ resistant and an inorganic metal oxide into the polymer thin film; (c) forming the selective infiltration thin film.

In practical applications, the selective infiltration thin film can be a protection material for biological and chemical protection or environment protection. The casting method is used to mix the Polyethyleneimine (PEI) and the Polyvinyl Alcohol (PVA) to form the polymer thin film having an interpenetrating network structure and gas permeability. The inorganic metal oxide can be Polyoxometalate (POM). The quantitative suspension test and the bacteriostatic ring test can be further used to test the germs resisting capability of the selective infiltration thin film, and the vapor permeability test and the chemical permeation experiment can be used to test the self-cleaning capability of the selective infiltration thin film.

Another embodiment of the invention is a selective infiltration thin film. The selective infiltration thin film includes a Polyethyleneimine (PEI), a Polyvinyl Alcohol (PVA), a germ resistant (e.g., a metal silver), and an inorganic metal oxide. Wherein, a Polyethyleneimine (PEI) and a Polyvinyl Alcohol (PVA) of appropriate ratio are used to make a polymer thin film, and the metal silver and the inorganic metal oxide are added to form the selective infiltration thin film.

In practical applications, the selective infiltration thin film can be a protection material for biological and chemical protection or environment protection. The casting method is used to mix the Polyethyleneimine (PEI) and the Polyvinyl Alcohol (PVA) to form the polymer thin film having an interpenetrating network structure and gas permeability. The inorganic metal oxide can be Polyoxometalate (POM). The quantitative suspension test and the bacteriostatic ring test can be further used to test the germs resisting capability of the selective infiltration thin film, and the vapor permeability test and the chemical permeation experiment can be used to test the self-cleaning capability of the selective infiltration thin film.

Above all, the invention uses a Polyethyleneimine (PEI) and a Polyvinyl Alcohol (PVA) of appropriate ratio to make a polymer thin film, and the metal silver and the inorganic metal oxide are added to form the self-cleaning selective infiltration thin film. Since the metal silver can effectively resist the bacteria, viruses, fungi, and fungal, and the inorganic metal oxide with photocatalytic activity can provide the organic pollutants catalysis and degradation effect, so that the metal silver and the inorganic metal oxide can be combined to obtain the selective infiltration thin film capable of resisting germs and self-cleaning.

After the further test, it can be found that the selective infiltration thin film provided by the invention will have good effect of resisting and protecting biological bacteria and chemical poisons, so that it can be used as the protection material of bio-chemical/environment protection, for example, the fiber, the film, and the thin film, and made to be protection apparatus and clothing to assume the health and safety of the industry chemical processor, the medical worker, or the environmental cleaner.

The objective of the present invention will no doubt become obvious to those of ordinary skill in the art after reading the following detailed description of the preferred embodiment, which is illustrated in the various figures and drawings.

BRIEF DESCRIPTION OF THE APPENDED DRAWINGS

FIG. 1 illustrates a flowchart of the selective infiltration thin film manufacturing method of an embodiment of the invention.

FIG. 2(A) and FIG. 2(B) illustrate the chemical structure equations of Polyethyleneimine (PEI) and Polyvinyl Alcohol (PVA) respectively.

FIG. 3 illustrates a scheme diagram of the selective infiltration thin film of another embodiment of the invention.

DETAILED DESCRIPTION OF THE INVENTION

The invention provides a selective infiltration thin film capable of resisting germs and self-cleaning and a manufacturing method thereof.

In order to effectively improve the problems occurred in the prior arts to let the protection material have the self-cleaning effect, the catalyst which can be degraded by reacting with the poisons or the materials capable of killing bacteria and germs can be added into the protection material, so that the function of self-cleaning can be achieved. For example, the catalyst or germs resisting material can be added into the polymer material to produce a film or a thin film, or can be made to be fiber in the electrospray wire form, there is no limitation to its application types.

In addition, there are a lot of choices for the catalyst with the poison degrading effect, for example, the nano metal oxide of degrading organic pollutants or Polyoxometalate of degrading organic pollutants by light; as to the germs resisting material, the polyoxometalate or silver having good germs resisting ability can be added to effectively resisting bacteria, viruses, mold, and fungus, such as escherichia coli and aureus. Therefore, it is a good choice to use Polyoxometalate to manufacture the protection material to have both effects of degrading poisons and resisting germs. After the catalyst and the antibacterial substances are added into the protective material, not only the protection ability of protection material can be enhanced, but also the self-cleaning effect can reduce the harm when the protection equipment are removed and the inherent danger when the cleaning staff washing it, so that the using life of protection equipment can be increased and the logistical cost and burden can be also significantly reduced.

An embodiment of the invention is a selective infiltration thin film manufacturing method. As shown in FIG. 1, at first, in step S10, using a Polyethyleneimine (PEI) and a Polyvinyl Alcohol (PVA) of appropriate ratio to make a polymer thin film. The chemical structure equations of PEI and PVA are shown in FIG. 2(A) and FIG. 2(B).

PEI and PVA will be simply introduced as follows. PVA is a common water-soluble polymer and has good properties of film forming, adhesive, emulsion, solvent resistance, and oil resistance. PVA thin film has good oxygen infiltration protection property under lower humidity; it can be 2 to 4 times to LDPE. For example, the same oxygen infiltration protection property can be achieved by the PVA film of width 10 μm and the LDPE film of width 37 μm.

Since the PVA and PP mixed polymer thin film has better gas stopping ability 130 times to the pure PP thin film, and the oxygen penetrating rate of the modified Polyamide (PA) thin film is 20 times to the PVA thin film, therefore, PVA and PA can be doped to increase the gas stopping property of the PA. As to Polyethyleneimine (PEI), PEI is a polymer with an amino dendritic structure. Since amine is a highly reactive nucleophilic functional group, therefore, the PEI has been widely used in the applications of adhesive, coatings, textiles, food packaging, and cosmetics.

In practical applications, the casting method is used to mix the PEI and the PVA to form the polymer thin film which is tough and soft. Since the PEI and the PVA will form an interpenetrating network structure in the polymer thin film, its moisture is about 10% and there are a lot of intermolecular hydrogen bonds existed in the polymer thin film.

Next, in step S12 and S14, the method adds a germ resistant (the metal silver) and an inorganic metal oxide into the polymer thin film to form the selective infiltration thin film. Wherein, the germ resistant (the metal silver) is used to provide the germs resisting ability of the selective infiltration thin film, and the inorganic metal oxide is used to provide the organic pollutant resisting ability. In fact, except the metal silver, the germ resistant can be any other matter having the ability of resisting/killing germs. The inorganic metal oxide can be Polyoxometalate (POM) and has no limitations.

In practical applications, the germs resisting material is formed by adding the germ resistant to the material. In general, it is not necessary for the germ resistant to kill the germs rapidly; on the contrary, it focuses on suppressing the growth and reproduction of the germs in long term using period to protection the health of human body. Generally speaking, the germ resistant can be divided into several types of inorganic, organic, and natural. The inorganic germ resistant can be further divided into a metal ion type germ resistant, a light catalytic type germ resistant, and a composite germ resistant. The metal ion type germ resistant uses the germs resisting ability of the metals silver, copper, or zinc to fix the metals silver, copper, zinc, or their ions on the surface of the porous material (e. g, zeolite, silica gel) through the physical adhering method and the ion exchanging method to make the germ resistant. Then, after the germ resistant is added into the product, the germs resisting material will be obtained.

The germs resisting mechanism of the silver inorganic germ resistant used in the invention is mainly concentrated on the germs resisting ability of the silver ion (Ag⁺). When the silver ion (Ag⁺) contacts with the microbial membrane, because the coulomb attraction force make the negative-charged cell membrane firmly combined with the silver ion (Ag⁺), the silver ion (Ag⁺) will penetrate the cell wall into the cell and react with the hydrogen sulfur functional group to destruct the activity of cell synthase, so that the cell will lose the ability to proliferate cell and died. After the cell is killed by the silver ion (Ag⁺), the silver ion (Ag⁺) will get out of the dead cell and contact with other cells to repeat the above-mentioned reactions. Therefore, the silver ion (Ag⁺) can continuously kill the germs for a long period of time.

In fact, the application range of the silver germ resistant is very wide. Various manufacturing methods can be used to mix the silver germ resistant with different polymers make the fiber, the plastic material, or the painting material. Since the main effect of the silver germ resistant is to contact the germs and kill them, therefore, the silver germ resistant as an adder should be uniformly distributed on the surface of the product. Because the inorganic germ resistant has advantages of safety, heat resistance, and durability, therefore, it is mostly suitable for the life products such as fiber, plastic, and construction materials. Thus, the invention uses the silver germ resistant as the germ resistant added into the selective infiltration thin film.

Then, the inorganic metal oxide added into the selective infiltration thin film will be discussed. The inorganic metal oxide used in the invention belongs to polyoxometalates, also called heteropoly acid compounds, and is the poly-metal-oxide clusters formed by the simple condensation of the inorganic oxygen-containing acid. Because the intermediate product having oxidation inhibition ability will be generated during the process of the organic matter decomposition by titanium dioxide (TiO₂), therefore, the photocatalytic material having different operation mechanisms (e.g., the polyoxometalate having similar catalytic ability to TiO₂) should be cooperated.

In practical applications, the polyoxometalates can be applied to photocatalytic decomposition of organic pollutants in water, for example, using K₄W₁₀O₃₂, H₃PW₁₂O₄₀, H₄SiW₁₂P₄₀, K₄SiW₁₂O₄₀, K₆[H₂O Mn^(II)SiW₁₁O₃₉], and K₆[H₂OCu^(II)SiW₁₁O₃₉] as photocatalyst to effectively decompose organic compounds such as a chloroacetic acid, a p-cresol, a methyl chloroform. In addition, the polyoxometalate can be applied to the fuel cell, such as H₃PMo₁₂O₄₀ and H₃PW₁₂O₄₀ can be reacted with CO poisoning the catalyst of the fuel cell. The polyoxometalates after the reduction reaction can be processed by a re-oxidation reaction on the positive pole of the fuel cell to generate power. It should be noticed that the polyoxometalates also has bioactivity, especially shows a very high activity and selectivity in anti-virus aspect. There are a lot of reference documents point out that the polyoxometalates have activities of anti-HIV, anti-cancer and anti-influenza virus. Therefore, the invention adds the inorganic polyoxometalates into the selective infiltration thin film to provide the function of anti-virus.

After the selective infiltration thin film is formed, the method can further uses the quantitative suspension test and the bacteriostatic ring test to test the germs resisting capability of the selective infiltration thin film, and the sulfur poisons can be selected to perform the vapor permeability test and the chemical permeation experiment to test the self-cleaning capability of the selective infiltration thin film.

In this embodiment, the germs resisting ability of the selective infiltration thin film uses the staphylococcus aureus (8099 ATCC 25923), the bacillus subtilis, the pseudomonas aeruginosa (8099 ATCC 27853), and the Escherichia coli as the target germ. The Mueller Hinton Broth (MHB) is used to nurture strains and at 37° C. overnight aerobic cultivation in a thermostat incubator. On the other hand, different proportions of Polymer/Ag and Polymer/POM are added into the culture medium in an incremental way to perform a series of dilutions. At last, the observed germs are inoculated in the medium under the germ concentration of 10⁷ cfu (number of germs)/ml to observe that what concentration of the Polymer/Ag and the Polymer/POM can stop the growth of the germs (Minimum Inhibitory Concentration, MIC) or kill the germs (Minimum Bactericidal Concentration, MBC). Therefore, the quantitative suspension test and the bacteriostatic ring test can be used to test the germs resisting capability of the composite material.

The invention mixes PEI, PVA, POM, and Ag to make the selective infiltration thin film and the anti-bacterial fabric to test the effects of permeability, antibacterial activity, and oxidation degrading poisons of the selective infiltration thin film. According to the test result, it can be found that Polymer/POM and Polymer/Ag thin film and weaving have permeability, and its germs resisting ability comes from the NH₂ of PEI, the germ killing mechanism of POM negative charge and the Ag ion. Selective permeability films show a very strong anti-bacterial characteristic to E. coli, staphylococcus aureus, pseudomonas aeruginosa, and bacillus subtilis. As to the aspect of anti-virus, not only the selective infiltration film oxygenates the poisons to the non-poison matters, but also the NH₂ of PEI also has the function of catching poisons, and the change of the color can achieve the alert effect. Therefore, the selective infiltration film has the ability of resisting germs and oxygenating the poisons to achieve the self-cleaning function and the protection function. Thus, the selective infiltration film of the invention has great developing potential to be used as germs resisting and bio-chemical protection material in the future.

In the thin film germs resisting characteristic test, the bacteriostatic circle is used to do the qualitative test; the steps are described as follows. After a wafer paper spindles (6 mm) is sterilized at 120° C., the wafer paper spindles will be immersed into the Polymer/POM and Polymer/Ag solutions. Then, the immersed wafer paper spindles will be disposed in the vaccinated strain (10⁵ cfu/ml) Mueller Hinton ager (MHA) disk. Afterward, it will be trained 24 hours in the constant temperature incubator at 37° C., and the size of its bacteriostatic circle will be measured. The test results are shown in Table 1 to Table 4.

TABLE 1 the size of the bacteriostatic circle of Polymer/POM thin film germs resisting experiment (mm) Poly- Polymer/ Polymer/ Polymer/ Polymer/ Strain mer POM-3 POM-5 POM-8 POM-10 Escherichia coli 10.97 11.75 12.10 12.39 12.84 Pseudomonas 13.49 13.61 13.61 13.86 14.26 aeruginosa Staphylococcus 13.73 13.78 13.98 14.03 14.45 aureus Bacillus subtilis 14.09 14.26 14.52 15.22 15.63

Table 1 shows the results of the qualitative test experiment of the bacteriostatic circle using the Polymer/POM thin films of different proportions to Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, and Bacillus subtilis respectively. From the results shown in Table 1, it can be found that the Polymer without POM also has the germs resisting effect. It is mainly because that the functional group —NH₂ on the PEI can have the germs resisting effect. With the increasing of the proportion of POM in Polymer/POM, the bacteriostatic circle will also become larger to prove that POM has a certain degree of germs resisting effect, and the effect is especially obvious to the Gram-positive bacteria such as Staphylococcus aureus, and Bacillus subtilis. This obvious effect is caused by the negative-charged POM(PV₂Mo₁₀O₄₀ ⁵⁻).

TABLE 2 the size of the bacteriostatic circle of Polymer/Ag thin film germs resisting experiment (mm) Poly- Polymer/ Polymer/ Polymer/ Polymer/ Strain mer Ag-0.3 Ag-0.5 Ag-1 Ag-3 Escherichia coli 10.38 11.96 12.46 13.51 15.75 Pseudomonas 10.31 12.95 14.15 15.12 17.11 aeruginosa Staphylococcus 10.35 11.34 12.55 13.42 17.81 aureus Bacillus subtilis 10.30 12.50 13.43 14.85 16.24

Table 2 shows the results of the qualitative test experiment of the bacteriostatic circle using the Polymer/Ag thin films of different proportions to Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, and Bacillus subtilis respectively. From the results shown in Table 2, it can be found that with the increasing of Ag in the Polymer, the bacteriostatic circle will also become larger in a certain degree to prove that Ag has a certain degree of germs resisting effect.

Comparing the above-mentioned Table 1 and Table 2, it can be found that the Polymer/Ag thin film has better germs resisting effect than the Polymer/POM thin film. No matter the Gram-positive bacteria or negative bacteria, the Polymer/Ag thin film has good germs resisting effect. That is to say, the metal silver (Ag) added into the selective infiltration thin film can effectively provide good germs resisting effect to the selective infiltration thin film.

TABLE 3 the size of the bacteriostatic circle of Polymer/Ag nonwoven cloth germs resisting experiment (mm) Poly- Polymer/ Polymer/ Polymer/ Polymer/ Strain mer Ag-0.3 Ag-0.5 Ag-1 Ag-3 Escherichia coli 14.13 15.84 16.75 17.42 19.37 Pseudomonas 14.93 16.17 17.68 18.23 22.81 aeruginosa Staphylococcus 18.35 18.82 18.97 19.55 22.59 aureus Bacillus subtilis 17.84 18.46 19.00 19.10 22.47

TABLE 4 the size of the bacteriostatic circle of Polymer/POM nonwoven cloth germs resisting experiment (mm) Poly- Polymer/ Polymer/ Polymer/ Polymer/ Strain mer POM-3 POM-5 POM-8 POM-10 Escherichia coli 14.64 15.74 16.12 16.16 17.97 Pseudomonas 16.12 16.36 16.82 17.58 18.08 aeruginosa Staphylococcus 15.78 17.67 17.97 18.16 19.53 aureus Bacillus subtilis 15.71 16.72 17.83 18.07 18.60

Table 3 and Table 4 show the results of the qualitative test experiment of the bacteriostatic circle using the Polymer/Ag nonwoven cloth and the Polymer/POM nonwoven cloth of different proportions to Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, and Bacillus subtilis respectively. From the results shown in Table 3 and Table 4, it can be found that after the Polymer/POM thin film and the Polymer/Ag thin film are combined with the nonwoven clothes, and the germs resisting effect can be still shown. With the increasing of the proportions of POM and Ag added into the Polymer, it can be found that the bacteriostatic circle will become larger in a certain degree, so that the effects of resisting the Gram-positive bacteria such as Staphylococcus aureus, and Bacillus subtilis are still obvious.

Another embodiment of the invention is a selective infiltration thin film. The selective infiltration thin film includes a Polyethyleneimine (PEI), a Polyvinyl Alcohol (PVA), a germ resistant (e.g., a metal silver), and an inorganic metal oxide. Wherein, a Polyethyleneimine (PEI) and a Polyvinyl Alcohol (PVA) of appropriate ratio are used to make a polymer thin film, and the metal silver and the inorganic metal oxide are added to form the selective infiltration thin film. The scheme diagram of the selective infiltration thin film is shown in FIG. 3.

In practical applications, the selective infiltration thin film can be a protection material for biological and chemical protection or environment protection. The casting method is used to mix the Polyethyleneimine (PEI) and the Polyvinyl Alcohol (PVA) to form the polymer thin film having an interpenetrating network structure and gas permeability. The inorganic metal oxide can be Polyoxometalate (POM). The quantitative suspension test and the bacteriostatic ring test can be further used to test the germs resisting capability of the selective infiltration thin film, and the vapor permeability test and the chemical permeation experiment can be used to test the self-cleaning capability of the selective infiltration thin film, but not limited to these cases.

Compared with the prior arts, the invention uses a Polyethyleneimine (PEI) and a Polyvinyl Alcohol (PVA) of appropriate ratio to make a polymer thin film, and the metal silver and the inorganic metal oxide are added to form the self-cleaning selective infiltration thin film. Since the metal silver can effectively resist the bacteria, viruses, fungi, and fungal, and the inorganic metal oxide with photocatalytic activity can provide the organic pollutants catalysis and degradation effect, so that the metal silver and the inorganic metal oxide can be combined to obtain the selective infiltration thin film capable of resisting germs and self-cleaning.

After the further test, it can be found that the selective infiltration thin film provided by the invention will have good effect of resisting and protecting biological bacteria and chemical poisons, so that it can be used as the protection material of bio-chemical/environment protection, for example, the fiber, the film, and the thin film, and made to be protection apparatus and clothing to assume the health and safety of the industry chemical processor, the medical worker, or the environmental cleaner.

Although the present invention has been illustrated and described with reference to the preferred embodiment thereof, it should be understood that it is in no way limited to the details of such embodiment but is capable of numerous modifications within the scope of the appended claims. 

1. An improvement on method of manufacturing a selective infiltration thin film, subject to a qualitative suspension test and a bacteriostatic ring test with a diameter D of a bacteriostatic circle, comprising the steps of: (a) mixing Polyethyleneimine (PEI) and Polyvinyl Alcohol (PVA) of an appropriate ratio for a polymer thin film; (b) adding an mount M of a germ resistant containing silver ion (Ag⁺) or an inorganic metal oxide, in particular, Polyoxometalate (POM) into the polymer thin film; and (c) forming the selective infiltration thin film; wherein there exists a positive linear correlation between the amount M and the diameter D of a bacteriostatic circle in the bacteriostatic ring test targeting bacstaphylococcus aureus (8099 ATCC 25923), bacillus subtilis, pseudomonas aeruginosa (8099 ATCC 27853), and Escherichia coli at a constant temperature 37° C., or equivalently, in Pearson's product-moment formula, M=r·D, where r represents a linear correlation coefficient, and 0<r<1.
 2. The method as claimed in claim 1, wherein in step (a), a casting method is applied for mixing Polyethyleneimine (PEI) and Polyvinyl Alcohol (PVA).
 3. (canceled)
 4. (canceled)
 5. (canceled)
 6. A selective infiltration thin film, subject to a qualitative suspension test and a bacteriostatic ring test with a diameter D of a bacteriostatic circle, made of: Polyethyleneimine; Polyvinyl Alcohol; an amount M1 of germ resistant containing silver ion (Ag⁺); and an amount M2 of inorganic metal oxide, in particular, Polyoxometalate (POM); wherein Polyethyleneimine and Polyvinyl Alcohol of appropriate ratio are used for a polymer thin film, the germ resistant containing silver ion (Ag⁺) or the inorganic metal oxide, in particular, Polyoxometalates (POM) is added for the selective infiltration thin film, and there exists a positive linear correlation between M1 μM2 and D, respectively, with D being obtained from the bacteriostatic ring test targeting bacstaphylococcus aureus (8099 ATCC 25923), bacillus subtilis, pseudomonas aeruginosa (8099 ATCC 27853), and Escherichia coli at a constant temperature 37° C.
 7. The selective infiltration thin film as claimed in claim 6, wherein a casting method is used to mix Polyethyleneimine and Polyvinyl Alcohol.
 8. (canceled)
 9. (canceled)
 10. (canceled) 